Process for the polymerization and copolymerization of olefins

ABSTRACT

OLEFINS AND DIOLEFINS ARE POLYMERIZED AND COPOLYMERIZED IN THE PRESENCE OF A CATALYST WHICH IS OBTAINED BY REACTING A TRANSITION METAL COMPOUND WITH MACROMOLECULAR NITROGENOUS COMPOUND WHICH IS SUBSTANTIALLY FREE OF HYDROXYL GROUPS AND THEN ACTIVATING THE THUS OBTAINED PRODUCT WITH AN ORGANOMETALLIC COMPOUND.

United States Patent Int. Cl. (50st /40 US. Cl. 260--80.78 10 ClaimsABSTRACT OF THE DISCLOSURE Olefins and diolefins are polymerized andcopolymerized in the presence of a catalyst which is obtained byreacting a transition metal compound with macromolecular nitrogenouscompound which is substantially free of hydroxyl groups and thenactivating the thus obtained product with an organometallic compound.

BACKGROUND OF INVENTION The present invention is directed to a processfor the polymerization of olefins and for the copolymerization ofolefins with one another and/or with diolefins in the presence of newsolid catalysts.

It has been proposed previously to polymerize ethylene in the presenceof a catalyst comprising an organometallic compound and a derivative ofa transition metal which are deposited on an inert support which may be,for example, preformed polyethylene (Belgian Pat. No. 552,550). In thisprocess, the catalyst is simply deposited on the surface of themacromolecular compound and may be eliminated therefrom by any physicalmeans such as by washing.

Another process for preparing catalyst consists in chemically bondingthe catalyst to a macromolecular compound having reactive groups. Anumber of catalysts capable of chemical bonding have been described inthe prior art.

One type of chemically bonded catalyst, the bonding of a derivative of atransition metal on a macromolecular support has been carried out bymeans of hydroxyl groups. French Pat. No. 1,405,371 is directed tocatalysts which are chemically bonded to a copolymer of vinyl alcoholcontaining 1 to mole percent of polymerized vinyl alcohol in itsmolecule. In the process described in French Pat. No. 1,475,927, of Feb.24, 1966, the macromolecular support on which the derivative of thetransition metal is chemically bonded is a hydroxylated polycondensationproduct derived from formol and an amino compound.

It has also been discovered that the bonding of the transition metalcompounds on macromolecular compounds can be carried out by using thereactive groups constituted by carbon-carbon double bonds, according toBelgian Pat. No. 681,400 of May 23, 1966.

SUMMARY OF INVENTION It has now been found that transition metalcompounds may also be bonded to nitrogenous macromolecular compoundswhich are free of hydroxyl groups. After activation of the resultingproducts with metals, hydrides, or organometallic compounds of Groups Ito III of the Periodic Table catalysts are obtained which are useful forthe polymerization of olefins and which exhibit very interestingproperties.

According to the present invention, the polymeriza- 3,553,181 PatentedJan. 5, 1971 tion of olefins and the copolymerization of olefins withone another and/or with diolefins is carried out in the presence of acatalyst which is the reaction product of one or more transition metalcompounds and a nitrogenous macromolecular compound which issubstantially free of hydroxyl groups. The nitrogenous compound isactivated by a metal, a hydride or an organometallic compound of themetals of Groups I to III of the Periodic Table.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The nitrogenous macromolecularcompounds which may be used in the process according to the inventioncontain less than 3% by weight of hydroxyl groups. They are preferablyselected from the group consisting of the compounds having amino, imino,amido, imido, urethane, nitrile and nitro groups. These reactive groupsmay be located on the lateral chain or, whenever possible, on the mainpolymeric chain. They may also be located in heter ocyclic nuclei.

The nitrogeonus macromolecular compounds which are preferably used toprepare the new catalysts are polyamides, polyurethanes, polyacrylamidesand polymers derived from a vinyl group containing heterocyclicnitrogenous compounds.

The transition metal compounds which may be used for the preparation ofthe new catalysts are preferably selected from the group consisting ofthe halogenated derivatives of the metals of Groups IVb, Vb and VIb ofthe Periodic Table and more particularly, the halides, oxyhalides andalkoxyhalides of titanium and vanadium. Examples of transition metalcompounds suitable for use in the preparation of the catalysts of thisinvention include titanium tetrachloride (TiC a), vanadium tetrachloride(VCl zirconium tetrachloride (ZrCl vanadium oxytrichloride (VOClchromium oxychloride (CrO Cl zirconium oxychloride (ZrOCl and titaniumtrichlorbutoxide (TiCl -,[OC H In addition, alkoxides and oxyalkoxides,such as titanium tetrabutoxide (Ti[OC H and vanadyl tributoxide (VO[OC Hand acetylacetonates, such as vanadyl acetylacetonate (VO[C5H702]2),chromium acetylacetonate (Cr[C H O and zirconium acetylacetonate (Zr[C HO also exemplify useful types of transition metal compounds which may beused in the preparation of the new catalysts. Combinations of two ormore of the above compounds may also be used, such mixed catalystshaving in some cases improved activities or properties over the simplecatalysts.

The mechanism of the reaction between the transition metal compounds andthe nitrogenous macromolecular compounds is not known with certainty.

However, it is believed that complexes are formed the structure of whichis similar to that of the well known complexes of the compounds of thetransition elements with some nitrogenous compounds such as with amines,amides, nitriles and nitro compounds.

In the preparation of the catalysts according to the invention, there isno quantitative formation of complexes between all the reactive groupsof the macromolecular compound and the transition metal compound. On thecontrary, the formation of complexes is limited to some specific siteson the surface of the macromolecular support.

Nevertheless, it has been observed that at the end of the reaction, thecompound of the transition element is chemically bonded to the supportand cannot be eliminated therefrom by physical means. For example, bywashing the reaction product of a transition metal compound and anitrogenous macromolecular compound with an inert solvent, such as ahydrocarbon which is a good solvent of the transition metal compound,the latter cannot be eliminated. On the other hand, a solvent having ahigh complexing power, for example tetrahydrofuran, which dissociatesthe resulting complex, as might be expected, would completely eliminatethe transition metal compound.

The reaction between the compound of a transition element and thenitrogenous macromolecular compound should be carried out in the absenceof moisture. For example, the reaction may be carried out by raising toits boiling point, the temperature of a suspension of the nitrogenousmacromolecular compound in a hydrocarbon, such as hexane, xylene,tetraline or carbon tetrachloride, containing dissolved therein, thetransition metal compound. The reaction may also be carried out bydirectly suspending the nitrogen containing macromolecular compound inthe pure transition metal compound when the latter is a liquid.

The reaction is generally carried out at a temperature between 20 and150 C. The temperature for the reaction is raised if at a lowertemperature insufficient bonding results. However, a temperature whichis too high may lead to degradation of the macromolecular compound.

The reaction product of a transition metal compound and the nitrogenousmacromolecular compound is carefully washed by using an anhydroushydrocarbon solvent until all traces of the transition element have beeneliminated from the washing solvent.

As a result, a solid catalytic complex is obtained which is insoluble inthe hydrocarbons and which is therefore particularly suitable for thepolymerization of olefins in hydrocarbon media to produce polymers assolid particles which are not dissolved in these media.

The solid catalytic complex should be activated by contact with a metal,a hydride or an organometallic compound of the metals of Groups I, IIand III of the Periodic Table. Trialkylaluminum and alkylaluminumhalides are particularly suitable activators. However, other metals,hydrides and organometallic compounds of particularly Groups Ia, Ila,IIb, and IIIa of the Periodic Table may be used, for example, butyllithium (LiC H diethylmagnesium (Mg[C H diethylzinc triethylaluminum(AI[C H tri n propylaluminum (AI[IIC3H7]3), triisobutylaluminum (Al[iC Hdiethylaluminum monochloride (Al[C H Cl), diisobutylaluminummonochloride (Al[iC H Cl), and diethylaluminum monobromide (Al[C H Br).

The activation may be carried out immediately before the introduction ofthe monomers. The catalyst may be matured for a more or less extendedperiod of time, at room temperature or at a higher temperature.

The process according to the prevent invention may be used for thepolymerization of olefins and the copolymerization of olefins with oneanother and/or with diolefins and particularly for the production ofpolyethylene, polypropylene, ethylene-propylene and ethylene-butadienecopolymers and terpolymers of ethylene, propylene and nonconjugateddiene. The new catalysts according to the invention, have increasedactivities and the polymers pro duced therewith have improvedproperties.

By using the catalysts according to the invention for the polymerizationof ethylene, it is possible to obtain a polyethylene having a highlinearity and a density higher the production of thermoplastic ethylenecopolymers having a low content of propylene.

, The new catalysts are particularly interesting for the production ofelastomeric copolymers of ethylene and propylene. They may be used forthe copolymerization of ethylene and propylene in the absence of solventwhen in admixture with the liquid monomers. The products so obtained arecharacterized by an amorphous structure and by excellent elastomericproperties, where as the products manufactured under similar conditionsby the use of known catalysts comprising the same organometallicactivator and the same compound of a transition element which is notbonded on a macromolecular compound have a noted crystallinity and arevery poor elastomers.

It has been found particularly advantageous to use mixed catalystsderived from titanium and vanadium which are jointly fixed on thenitrogenous macromolecular compound for the copolymerization of ethyleneand propylene and for the production of ethylene-propylenenon-conjugateddiene terpolymers.

The process according to the invention may be used for thecopolymerization of non-conjugated dienes with one or more monoolefinssuch as ethylene propylene or butene-l.

The non-conjugated dienes which may be used in the process according tothe invention may be selected from the following:

The non-conjugated aliphatic dienes, such as pentadiene-1,4,hexadiene-1,4, hexadiene-1,5.

The monocyclic dienes, such as 4-vinylcyclohexene, 1,3-divinylcyclohexene, cycloheptadiene-1,4, cyclooctadiene- 1,5.

The non-conjugated alicyclic dienes having an endocyclic bridge such asdicyclopentadiene and norbornadiene.

Particularly interesting terpolymers which may be used as sulphurvulcanizable elastomers and which may be obtained by using the newcatalysts according to the invention are theethylene-propylene-dicyclopentadiene and theethylene-propylene-hexadiene-1,4, terpolymers.

The catalysts according to the invention are also suitable for thecopolymerization of olefins with conjugated diolefins.

The polymerization and the copolymerization may be carried out accordingto any known procedures in the gaseous phase, in the absence of anyliquid medium which is a solvent of the monomer, or in the presence of adispersion medium in which the monomer is soluble. An inert hydrocarbonwhich is liquid under the conditions of polymerization or the monomeritself maintained in a liquid state under its saturation pressure may beused as liquid dispersion medium.

The following examples are given to further illustrate the best modecontemplated for carrying out the invention, but are not to beinterpreted as limiting or restricting, the scope of this invention inany manner whatsoever.

EXAMPLES 1 T O 5 (a) Example 1Preparation of catalyst Into a cylindricalreactor heated by means of a double jacket, provided with an agitatorand having a sintered glass plate at the lower portion thereof, therewere introduced 60 ml. of TiCl and 12 g. of a high molecular weightpolycondensation product derived from w-arninodecanoic acid, sold underthe trademark Rilsan 200. This product melts at 186 C. and has arelative viscosity of 1.39 when measured at 20 C. in a 5 g./l. solutionin sulphuric acid.

The suspension is maintained at a temperature of approximately 25 C. forone hour after which a solid product is separated and washed thoroughlywith anhydrous hexane until all traces of TiCL, have been elimi natedfrom the washing solvent.

The product is a clear yellow solid which contains 23 g. of titanium perkilogram.

(b) Example 2Polymerization Into a 3 liter stainless steel autoclavewhich has been dried and flushed with dry ethylene, there aresuccessively introduced 5 ml. of a solution containing 200 g. per liter6 The mixture is stirred and the temperature of the autoclave is raisedto 40 C. Ethylene is gradually introduced so as to obtain a constanttotal pressure of 19.2 kg./cm. The liquid phase contains 7.5 mole ofethylene per 100 mole of ethylene and propylene.

of tri n-propyl-aluminum in hexane, 565 mg. of the solid 5 catalystdescribed in Example 1 and 1 liter of pure, dry After two f the gases.are removed i fl autohexane clave, the resulting product is separatedand it is treated The mixture is heated at C and the ethylene Prey withwater vapor to eliminate dicyclopentadiene. The sure is raised kg./cm.The pressure is maintained 9 5? i g z i f th 1 constant by continuouslyintroducing ethylene. After two 10 F f e t o a erpo ymer 0 e y hours,the autoclave is opened and 115 g. of polyethylene 9}? g. c S 3 f t 1 hr is collected which corresponds to a catalytic activity of d 6 ca g gay 13 o erpo ymer Per 450 g. of PE/h.g. of Ti atm. C H Per The resultingpolyethylene was examined by infrared EXAMPLES 3 o 10 spectro-analysis.It contalns less than 1 methyl group, 15 less than 0.01 transinternaldouble bond, 0.07 vinyl double (3,) Example 8-Preparation of catalystbonds and 0.01 vinylidene double bonds per 1000 carbon atoms. 9.1 g. ofthe polyamide used in Example 1 are com- 4 C bined with 40 ml. of TiCl,and 11.2 ml. of VOCl The (c) F' 3 and opolymenzatlon mixture ismaintained at C. for minutes. It is a 5 11ml Stalnless Stee} autoclavedried a flushed washed carefully with 1 liter of hexane and dried underWlth P pyl there w llfifodllced Solution of 100 vacuum. There isobtained a catalyst having bonded g./l. of triisobutylaluminum 1nhexane, the product prethereon 4 5 f c and 7,1 of voc Per kg of pared asin Example 1, hydrogen at a partial pressure of h i 0.2 kg./cm. and1.116 kg. of propylene. The mixture is 25 heated to 40 C. whileintroducing ethylene in order to (b) Example 9-Copolymerization providea total pressure of 19.3 kg./cm.'-. The result is a solution containing7.5 mole percent of ethylene in liquid 1.89 g. of this catalyst and0.500 g. of triisobutylpropylene. aluminum are used for thecopolymerization of ethylene After four hours, the gases are removedfrom the mon 30 and propylene under the conditions described in Exammerswhich have not react d and a o ly f th l pics 3 and 4. After a reactionperiod of 4 hours, there IS and propylene is collected. obtained 562 g.of a copolymer having a propylene con- The reaction conditions and thedata concerning the tent of 52 mole percent. The activity of thecatalyst exresulting products are given in Table 1 below. pressed asabove is 1800.

TABLE 1 Solid catalyst Catalytic Propylene Weight of activity, contentTotal T1014 copolymer g. 00- of copolcontent, content, Al (iBu)produced, polymer, ymer, mole g. mg. g. g. g. TiG14.h percent Sample NoEXAMPLES 5 TO 7 45 (0) Example 10-Terpolymerization (a) Example5-Preparation of catalyst 0.674 g. of the above catalyst and 0.31610l g.of Al(iliu) are used for the copolymerization of et y ene, propy ene gg'g i g g f i i 5 2 3 'i 'g 2; g i gi and dicyclopentadiene under theconditions set forth in s 3 hexane. The mixture is maintained at atemperature of lib-(ample After one hour and 59 mmutes there IS ob otamed 114 g. of a terpolymer. This terpolymer was vul- 25 C. for 10minutes. A solid is separated and Washed 1 t extensively with hexaneuntil all traces of VOCl in the :Ei by i i i contamlgg-vu g i i l eactivity 0 t e ca a ys expresse in g. o erpo yme EVgZllfiijglXglifigV6been eliminated and the product is producfid Per hour and per f h nd ofthe There is obtained'a dark brown Solid catal St C transition elementsis 2680. The propylene content of the 71 4g of VOCI er kilo ram y 0 mmgproduct is 43 mole percent and its unsaturation is 0.25

- 3P g (:0 groups g./kg.

b Exam 1e 6Co ol merization of eth lene d p g g y an EXAMPLE 11 Thecopolymerization of ethylene is carried out under 7.8 9 Of a powderedpolycon l P Q defived the conditions set forth in Examples 3 and 4 byusing from adipic acid and hexamethylene diamine having a 1.369 g. ofthe solid catalyst prepared in Example 5 and melting point of 250 C. andsold under the trademark 0.500 g. of triisobutylaluminum. Ultramid A 3 Kby BASF were dried for two hours under After 4 hours, there is obtained39 g. of a copolymer of vacuum at 60 C. The powder is lntroduced with 50ml. ethylene and propylene containing 42 mole percent of of pure TiCL,into the apparatus described in Example 1. propylene. The activity ofthe catalyst, expressed in g. of The mixture is stirred and heated up to100 C. durlng the copolymer produced per g. VOCl used and per one hourand the reaction is earned out for one more hour is of 100. hour at thistemperature. 1 d h f The mixture is cooled, the so id is separate t ererom (c) Examp 1e 7 cOp01yIg-e nziltlon i f Wlth and is washed thoroughlywith hexane until all traces of propylene and lcyc openta mm thechloride in the washing solvent have disappeared. Into a. 1.5 literautoclave, dried and flushed with pro- The catalytic complex contains 72g. of Ti and 210 g. of pylene, there were successively introduced 0.830g. of C1 per kilogram, which corresponds to an atomic ratiotriisobutylaluminum in solution in hexane, 1.550 g. of the chlorine/titanium of 3.95. catalyst prepared according to Example 5, 10.5 g. ofdi- 75 0.158 g. of this catalyst and 0.500 g. of Al(1Bu) arecyclopentadiene and 338 g. of liquid propylene.

used for the copolymerization of ethylene and propylene EXAMPLE l2 5 g.of a polyamide similar to the one used in Example 11 Were dried under avacuum at 60 C. for two hours and the resulting powder is introducedinto an apparatus as described in 'Example 1. ml. of pure VOCl are addedthereto and the reaction is carried out for a period 8 aluminum hasresulted in 140 g. of a copolymer containing mole percent of propylene.The catalytic activity is 604 g. of the coploymer per g. of TiCl and perhour.

EXAMPLES 14 TO 19 (a) Examples l4l9-Preparation of catalysts Catalystswere prepared by reacting nitrogen containing polymers with TiCl in anapparatus and according to the process described in Example 1. Thereaction conditions and the properties of the resulting products aregiven in Table 2 below.

TABLE 2 Titanium Nitrogenous polymer content Quantity Reaction Length ofafter the ofbounded Quantity, TiCli, temperareaction, reaction, TiOli,Formula Name g. ml. ture, 0. min. g./kg. gJkg.

Example No.1

14 OHZCH Polyacrylamide (American 2. 74 30 60 2 8 L Cyanamid).

CONIIQ n 15 -ECI'I2CH] Poly(acrylonitrile)* 9.8 50 60 4.3 17

l6 ll. 5 5O 8O 60 15 59. 4

(BA F) Polyvinylgarbazole, Luviean M Obtained by suspensionpolymerization in the presence of lauroyl peroxide at 60 C. for 3 hours.Intrinsic viscosity measured at 20 C. in dimethylformamide: 0.75 l./gr

(b) Examples l7-19Copolymerization of ethylene and propylene The solidcatalysts as prepared in (a) have been used to carry out thecopolymerization of ethylene and propylene under the conditionsspecified in Examples 3 and 4.

The specific reaction conditions and the characteristics of theresulting products are given in Table 3. below.

TABLE 3 Catalyst Activity Propylene of content Preparation Weight ofcatalyst, of the according Total Quantity copolymer, g. of cocopolymer,to Example quantity, of TiCli, Al(iBu)i, produced, polymer, mole No. g.mg. g. g. g. TiCl4.h percent Example No.:

After four hours, there is obtained 88 g. of a coploymer containing 27mole percent of propylene.

The catalytic activity is 214 g. of copolymer per hour and per g. ofVOCl EXAMPLE l3 6 g. of a polyurethane produced from butanedio1-l,4 andhexamethylene diisocyanate and which melts at C. are dried under vacuumfor a period of one hour at -60 C. This product is sold by Bayer underthe trademark Durethan U0.

A suspension of the dried powder in 60 ml. of TiCl is formed and themixture is stirred and heated to 85 C. during one hour. The suspensionis maintained at that temperature for a period of one hour and isthereafter cooled. The solid is separated and washed thoroughly withpure, dry hexane before drying it.

The product contains 46 g. of Ti and 130 g. of Cl per kilogram whichcorresponds to an atomic ratio Cl/Ti of 3.82.

The copolymerization of ethylene and propylene under the conditions setforth in Examples 3 and 4 with 0.318 g. of the above solid catalyst and0.700 g. of triisobutyl- What we claim and desire to secure by LettersPatent 1. Process for the polymerization and the copoly-merization ofolefins and non-conjugated dienes wherein the reaction is carried out inthe presence of a catalyst consisting essentially of the reactionproduct of at least one transition metal compound and a solidnitrogenous macromolecular compound free of hydroxyl groups which isselected from the group consisting of polyamides, polyurethanes,polyacrylarnides and poly(vinyl-substituted nitrogen heterocyclic)compounds, said reaction product being activated by a metal, a hydride,or an organometallic compound of the metals of Groups I to III of thePeriodic Table.

2. Process according to claim 1 in which said transition metal compoundis selected from the group consisting of halides, oxyhalides,alkoxyhalides, alkoxides, oxyalkoxides and acetyl acetonates.

3. Process according to claim 1 in which the transition metal compoundsare halogenated derivatives of the metals of the Groups IVb, Vband VII)of the Periodic Table.

4. Process according to claim 1, in which the compounds of thetransition In l are selected from the group consisting of halides,oxyhalides and alkoxyhalides, alkoxides, oxyalkoxides and acetylacetonates of titanium and vanadium.

5. Process according to claim 1 in which the activator is an alkylaluminum or an alkyl aluminum halide.

6. Process according to claim 1 in which the reaction is thepolymerization of ethylene, propylene and butene.

7. Process according to claim 1 in which the reaction is thecopolymerization of ethylene and propylene.

8. Process according to claim 1 in which the reaction is thecopolymerization of ethylene, propylene and a nonconjugated diene.

9. A hydrocarbon insoluble polymerization catalyst comprising thereaction product of a transition metal compound and a solid nitrogenousmacromolecular compound free of hydroxyl groups which is selected fromthe group consisting of polyamides, polyurethanes, polyacrylamides 10and the polymers derived from vinyl substituted nitrogen heterocycliccompounds.

10. A polymerization catalyst which comprise the reaction productprepared by activating the catalysts defined in claim 9, with a metal, ahydride or an organometallic compound of the metals of Groups I to IIIof the Periodic Table.

References Cited UNITED STATES PATENTS 3,396,155 8/1968 Toussant et al26080.78

JOSEPH L. SCHOFER, Primary Examiner R. S. BENJAMIN, Assistant ExaminerU.S. Cl. X.R.

